Germanium, because
of its unique performance, has been widely used in the manufacture
of optical fiber. Recycling germanium is significant because of geographical
scarcity and technical barriers. In this study, a novel low-vacuum
phosphate reduction process of GeO2 was proposed to recover
germanium from optical fiber scraps. The thermodynamics, kinetics
model, product analysis, and reaction mechanism were studied. Thermodynamic
results indicated that the decomposition products were mainly the
P(V) compounds Na4P2O7 and Na5P3O10, PH3, O2, and H2. The reaction order models of dα/dt = 1.44 × 108 exp(−212000/8.314T)(1 – α)3.63 min–1 can describe the kinetic results of the phosphate reduction process
well. The average activation energy E̅
α located around 212 kJ mol–1. The
chemical species of Ge in the condensed products were metal Ge, Ge(II),
and a small amount of Ge(IV) by XPS analysis. A hydrolysis reaction
followed by a nucleophilic addition–elimination mechanism can
explain the decomposition of NaH2PO2. Then,
a mechanism of collapse of the GeO2 octahedron by the action
of PH3(g) and H2 was presented to clarify the
formation of Ge and its oxides. Finally, a nucleation mechanism under
low-vacuum conditions explained the distribution of condensed products.
We quantitatively investigated the vacuum phosphate reduction process
and can successfully guide germanium recovery from optical fiber scraps.